Nonclogging distillate fuel oil



Patented Dec. 25, 195i 2,579,890 NONCLOGGING DISTILLATE FUEL OIL No Drawing. Application July 3, 1948, Serial No. 37,084

13 Claims.

bon fuels, and more particularly to fuel oil compositions capable of preventing or inhibiting the sludging and/ or clogging tendencies generally exhibited by hydrocarbon fuels, such as those utilized in burner systems, tanks, diesel and combustion engines, and various other industrial and domestic equipment. In addition, this invention relates to fuel compositions capable of removing preformed deleterious matter from filters, screens, and the like, caused by deterioration and/or the presence of foreign bodies e. g. water in fuel oils.

Hydrocarbons, such as distillate fuels, for example, those having a normal distillation range of from about 300 F. to 750 F. and particularly those fuels having a distillation range of from about 340 F. to about 640 F., generally have a marked tendency to deteriorate under oxidizing conditions, and to form sludge. Also, the presence of impurities in such fuels, such as the presence of moisture, dispersed water, organic and/or inorganic foreign matter, and the like, cause the formation of insoluble products, which tend to settle out and adhere to surfaces'with which they come in contact, thereby in turn, causing clogging or plugging of filters, strainers, screens, conduit lines, and the like, of the equipment in which they are used. This necessitates frequent cleaning and even replacement of parts, thereby markedly decreasing the performance efficiency of various equipment which utilizes such fuel oils.

The problem of screen clogging is common, particularly in domestic fuel oil systems employing distillate fuel oils produced by distilling or cracking of petroleum which fuels are characterized by their relatively low viscosity and other properties. Fuel oils of this type generally conform to the specifications set forth in Commercial Standards C. S. 12-40 for Nos. 1, 2, and 3, fuel oils. Petroleum distillates within the ranges specified and which generally do not exceed 750 F. and preferably are below 675 F. for use as diesel fuels are further examples of the type of oils which under conditions described have a tendency towards screen or filter clogging, particularly when they contain minor amounts of water dispersed therein.

Another place where screen clogging and plugging of conduit lines is encountered is in storage tanks for fuel oils, which tanks may be connected to the burner systems or engines, etc. The stored fuel generally comes in contact with air, moisture, water, etc., which causes formation and precipitation of sludge materials which in turn settle out and deposit on and clog the screens or filters used for protecting the burners or engines which use such oils as the fuel.

It is an object of this invention to inhibit sludging tendencies of hydrocarbon fuel oils. It is another object of this invention to inhibit sludging and precipitation of contaminants in hydrocarbon distillate fuel oils, and particularly in cracked hydrocarbon fuels. It is still another object of this invention to provide distillate fuel'oils and particularly fuel oils obtained during cracking of hydrocarbons, which fuels' have excellent performance characteristics with respect to freedom from screen clogging, even after extensive storage under oxidizing conditions and in the presence of water. Still another object of this invention is to provide a distillate fuel oil composition which is effective in removing preformed sludge deposits formed in fuel oil systems. Still another object of this invention is to provide a particular type of distillate fuel'oil compositions, and blends thereof, which are non-corrosive and stable, and which are effective for cleaning and sludge removing.

The above and other objects of this invention may be attained by dispersing or dissolving in a hydrocarbon distillate fuel oil (which normally have a tendency to cause clogging or plugging of screens, filters, conduit lines and the like) a I treated or untreated cracked fuel oils, or mixtures of cracked fuels with straight run fuel oils, having components normally distilling at about 500 F. and having an end distillation point not exceeding "750 F. Generally such fuels of the type under discussion have a boiling range of from about 340 F. to about 700 F. and preferably have a boiling range of from about 400 F. to about 675 F.

Cracked fuels may be obtained by thermal or catalytic cracking of certain petroleum hydrocarbon feed stocks. Both the cracked fuels as well as blends of cracked and straight run fuels, may be acid and/or caustic treated to improve their stability. Specifically, hydrocarbon distillates which are utilized as bases in compositions of this invention are cracked gas oils, fuel oils, furnace oils, burner oils, diesel fuel oils, kerosene,

etc., and mixtures of said cracked fuels with the I corresponding or like straight run hydrocarbon fractions, e. g. fuel oils, etc.

The properties of a caustic treated catalytically cracked light gas oil and a 50-50 blend of an untreated catalytically cracked light gas oil and a straight run acid treated gas oil which have a marked tendency towards clogging screens, etc. are given in the following table:

505 i Blend of Catalyt- C t 1 n ically cracked light a a y y Pmmmes 0115 on and Strai ht 813 55 Lght Run Light Gas Oil Gravity, API 32. 6 31. 0 ASTM Dist F) IBP 414 434 EBP 664 620 Sulfur Per Cent. W. 0. 839 0. 788 Conradson Carbon Residue (10% Btms) (Per Cent W) 0.01 0.01 Poui Point, F. --5

The surface active agents which possess the unique property of inhibiting sludge formation or removing preformed deposits from surfaces thereby preventing clogging of systems utilizing fuels normally susceptible of causing such deterioration are salts of organic acidic compounds containing a sulfo radical or radicals represented specifically by the following class of compounds:

IA. Salts of sulfopolycarboxylic acid esters such as are fully and clearly described in U. S. Patents, 2,028,091 and 2,176,423, and which may be broadly defined as derivatives of esters of aliphatic dibasic acids having the formula 'coox COOX wherein R is an alkyl radical containing at least one sulfonic group and X is hydrogen or an alcohol or phenol radical not connected by a carbon to carbon bond with R, at least one X being such an alcohol or phenol radical.

These sulfocraboxylic acid esters may be in the form of salts of alkali, alkaline earth or heavy metals such as Na, K. Li, Ca, Ba, Sr, Mg, Zn, Al. Sn, Cd, Cr, Sn, Ni, Fe or in the form of salts with ammonium or other amine bases. Specific acids used to form these compounds may be sulfosuccinic, sulfoadipic, sulfoglutaric, sulfosuberic, sulfofumaric, sulfomalonic and other sulfodicarboxylic acids. Examples of specific compounds are: dioctyl sodium sulfosuccinate, diamyl sodium sulfcsuccinate, dicapryl sodium sulfosuccinate, difurfyl sodium sulfosuccinate, dioctyl sodium sulfoadipate, dioctyl sodium sulfomalonate, etc. The amount of salt used may vary from about 2% to and preferably between about 4% and 8%.

IB. Salts of alkyl esters of monocarboxylic aromatic sulfonic acids having the general formula:

wherein Ar is an aryl nucleus derived from hydrocarbons such as benzene, naphthalene, diphenyl and the like; X is a substituent such as hydrogen, hydroxyl, hydrosulfide, halogen and the like; Y is an alkali, alkaline earth or heavy metal such as Na, K, Li, Ca, Ba, Sr, Mg, Zn, Al, Ca, Cd, Cr, Sn, Ni, Fe; 11., m, and p, are WhQl? furic acid derivatives of isopropyl, normal butyl,

isobutyl, normal amyl alcohols, and ortho and/ or para hydroxy diphenyl, etc.

If desired, and under certain conditions of use, it is preferred to add detergents to compositions of this invention. The function of the detergent agents in compositions of this invention appear to act as peptizers, to aid in inhibiting or preventing the settling and adhering of impurities and sludge to surfaces, and to allow any impurities present or formed to pass through the screen or filter system.

Detergents which may be used are alkali, alkaline earth and heavy metals and organic nitrogen base salts of various organic acids. The acidic portion of such detergents may be naphthenic acids, petroleum sulfonic acids, aromatic and hydroxy aromatic carboxylic acids, aliphatic acids, said acids containing, if desired substituent groups, e. g. amino, hydroxide, mercapto, halogen and sulfur groups and the like. Also phenates, alcoholates. carbamates, thiocarbamates, xanthates, etc., may be used.

Particularly preferred class of detergents are the salts of alkyl substituted phenol sulfides, or its selenide and/or its telluride equivalents. These phenolic salts may be represented by the general formulas XM lib-XE wherein M is a metal; R and R. represent at least one alkyl radical attached to the aromatic ring Ar, the total number of carbon atoms in all of such radicals being at least 5; X is O and/or 8; Q is S, Se or Te and n is an integer of from 1 to 4.

To form the salts of these phenolic compounds they may be treated with such metal compounds, as Li,'Na, K, Cu, Hg, Fe, Mn, Mg, Ca,.Ba, Sr, Pb, Ni, Co, Cr, Sn, Fe, etc. Alkaline earth metals are particularly preferred because of their solubility in hydrocarbons and potent detergent properties.

In addition to the normal salts of phen \lic compounds, basic salts may be used and can be represented by the formula m-xn m-xn n-L-mr-R' I wherein the symbols are the same as referred to in the previous formulas. These basic salts may be formedby reacting the aromatic acidic compound with more-than the amount of metal oxide or hydroxide necessary to form the normal salt.

Some specific compounds as represented by the above formulas are: barium tertiary octyl phenol sulfide and disulfide, barium di-tertiary amyl phenol sulfide, calcium iso-hexadecyl phenol sulfide, magnesium tertiary amyl phenol sulfide, cobalt tertiary amyl phenol sulfide, barium dodecyl salicylate sulfide, sulfide of the barium salt of the ethyl ester of p-hydroxy dithiobenzoic acid, calcium octyl phenol selenide, etc. The amount of detergent salt used may vary from between about and and preferably is kept below 10%.

In systems wherein substantial amounts of moisture are present, a drying agent may be added which is compatible with the active ingredients of this invention. By tying up most of the free moisture in this manner, the amount which would normally combine with sludge forming materials is diminished, thus alleviating a most aggravating clogging problem.

Ill)

Drying agentswhich are particularly suited are butylene glycol, diamylene glycol, ether alcohols .and particularly the glycol mono alkyl ethers,

e. g. the cellosolves such as ethylene glycol mono ethyl ether, ethylene glycol mono propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono iso-butyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol mono hexyl .ether, propylene glycol mono ethyl ether, propylene glycol mono isoamyl ether, etc. Also glycerine and the like may be used.

The amount of these drying agent materials, when used, constitutes a substantial portion of the base and generally is around about 50% or more. However, under certain conditions these materials may be omitted from the base.

A general formula of a base concentrate composition of this invention which will henceforth be referred to as Composition A may consist of:

COMPOSITION A General Range Limited Range Per Cent Per Cent Salt of a smile carboxylic acid ester or a sulio compound as listed under 13 or [C Dgtcergent e. g. Barium salt of an alkyl phenol sule Draying agent, e. g. diethyleneglycol monobutyl Specific base compositions may be illustrated by the following examples:

'I-hefollowing table further illustrates suitable anti-clogging base compositions of this invention:

Components 1 2 3 4 5 6 7 8 9 Surface Active Agent:

Dioctyl sodium sullosuocinate. x x x Dlamyl sodium sullosuccinate. Dicnpryl sodium suli'osuccina Dioctyl sodium sulfoadipate. x x Octyl-O-sodium sulfobenzoate. Di-n-hexyl ester of potassium sullophthnlic acid Detergent.

Bitii (51311. of alkyl phenol disul G I Ca salt of alk 1 pb nol d'sulfide (-a alkyl salicylat Na alkyl salicylate Na petroleum naphthenate. Ca petroleum naphthenate... Drying Agent:

Diethylene glycol monobutyl ether Diethylene glycol monoethyl ether Ethylene glycol monobutyl ether cetylene glycol Dipropylene glycol All of the above compositions are diluted with a hydrocarbon distillate fuel oil in amounts indicated above.

Compositions of this invention are added generally in amounts of 1 pint or less with from about 250 gallons to about 1000 gallons of fuel oil. Thus, for example, on a percentage basis of fuel used. one pint of such compositions described per 250 gallons of fuel would correspond to approximately the following concentration of the active ingredients in the final compositions:

Salt of a sulfocarboxylic acid ester or deriva tives thereof or compounds as noted under 113 and 10, 0.0025% to 0.005%; detergent (salt of an alkyl phenol sulfide), 0 to about 0.0025% or 0.0042%, drying agent (glycol-ether), 0 to 0.0265%.

Compositions B, C and D when added in amounts of approximately 1 pint per 250 gallons of fuel oil correspond to approximately the following concentrations of the active ingredients present in the final composition COMPOSITION B Per cent by weight I l7 oowosrmon Per cent by weight Dioctyl sodium sulfosuccinate 0.002 Barium salt of akyl phenol sulfide 0.0042 Hydrocarbon fuel oil Balance COLEPOSITION D Per cent by weight Dioctyl sodium sulfosuccinate 0.005 Barium salt of alkyl phenol sulfide 0.0042 Diethylene glycol monobutyl ether 0.0265 Hydrocarbon fuel oil Balance To inhibit corrosive tendencies of the nonpolar organic liquids a minute amount of caustic or aromatic nitrogen compound such as aniline may be added. These compounds act as alkaline reserves and render the fuel, or the hydrocarbon, substantially non-corrosive to copper, brass and other metals. v

To illustrate the eifectiveness of compositions of this invention as deposit removers. sludge inhibitors and corrosion inhibitors, particularly when the liquid treated has an alkaline reserve, the following tests were made which are self-explanatory.

Example I Two 50 cc. samples of a test fuel oil were strained through a 200 mesh screen, in order to remove any extraneous material, and placed in small bottles. To each sample was added 0.15 cc. of distilled water. One sample was retained as a control; the other was doped with a composition containing as active ingredients dioctyl sodium sulfosuccinate, barium salt of alkyl phenoldisulfide and diethyl glycol monoethyl ether; the total amount of the active ingredients in the doped oil was less than 0.05%. Samples were flow through the screen'between the doped and undoped oils served as a measure of effectiveness.

Composition Time gf g Remarks Undopediueloll. 1.800 seconds Screen presented a continuous mass of gelatinized and emulsified sludge which retarded flow of oil. Doped fuel oil... Lcssthan25seconds. Screen absolutely clean.

Example II Approximately 5 gallon samples of undoped and doped fuel oil as in Example I were clouded with steam and circulated'for 21 hours through a l00-mesh screen, by means of a conventional oil'bumer pump. The drop in flow, as measured by a rotameter placed in the stream, indicated added to about 250 gallons of oil as used in domestic oil burner installations. The strainers in several of the test burners, including the one used in the control test in which the oil was undoped, were thoroughly cleaned at the beginning of the tests. while the strainers in the remaining burners were not cleaned and the test was conducted for about 40 days after which the systems were inspected.

Test No. 1 2 3 Inspection at start of test.

Condition of strainers:

0. Main fuel line 7 r i lu zggd with 75% coated- 100% cov r d.

ac su ge. b. In Nozzle or Mag- Completelycovered plugged 100% covered netic Valve. with black sludge. with sludge. with sludge. Time gilnce strainer last Zmonths lmonth 6months.

cean

at beginning of Yes No Yes.

Amouhtofoil 500gallons 500gall0ns---- 500gailons. Amount of additive (Com- Non 1 quar 1 quart.

position C). Inspected at end of test:

Condition of strainers:

a. Main fuel line 50%plugge Clean Clean. 1:. Nozzle or Magnetic 75% covered with do Do.

Valve. black sludge.

agitated in a shaking machine for 5 minutes and E: m I then put aside for observation. p 6

Composition Observation (Initial) Moisture and particles of emulsion adhered tenaciously to sides of bottle. Black sludge particles dropped to the bottom.

Oil drained evenly and smoothly from side of bottle and solid particles were retained in suspension for a long time.

Undoped fuel oil.

Doped fuel oil.

After one hour standing samples were shaken for about 30 seconds and then allowed to flow by gravity through a 200-mesh screen one-fourth inch in diameter. The difference in the rate of tem and the condition of each specimen as well Per cent as appemme the and seal Alkali metal salt of an unsubstituted sulfoment corrosion, etc. observed. carboxylic acid t 2-10 Hydrocarbon distillate fuel oil Balance wnron'r Loss or 'rns'r SPECIMENB e serve 8118 an conspeclmens fieserve (Caustic) talnlng less than 0.05%

Composition C Total Cu Specimens, mg... 6.9 1.9 Total Brass Specimens, mg.- 17. 5 9.0 Total All Specimens, mg... 24.4 11.8

EFFECT OF FUEL OIL DOPED WITH COMPOSITION C 0N STRAINERS Specimens Alkaline reserved iuel Alkaline reserve oil contelm ing 1 pint of Composition C per 500 gallons oil 100% covered with Condition of main line st brown emulsion.

rams. Conditions of screen disks in Lower half slightly stained.

To compositions of this invention may be added minor amounts of a foaming inhibitor such as' silicon liquids, e. g. dimethyl silicone; fluoro organic compounds, fluoro paraflins, salts of alkyl alkylene Phosphates and the like. Compositions of this invention may be used to remove deposits, formed on metal surfaces such as in tubes, evaporators, heat exchangers, distillation and cracking equipment and the like. They are noncorrosive and do not interfere with the functioning of the fluid in which dispersed.

It is understood that while the features of the invention have been described and illustrated in connection with certain specific examples, this invention, however, is not to be limited thereto or otherwise restricted, except by the scope of the appended claims.

We claim as our invention:

1. An anti-clogging concentrate composition suitable for addition to hydrocarbon fuels containing substantial amounts of cracked components and normally susceptible toward clogging comprising:

Per cent Dioctyl sodium sulfosuccinate 4.0 Hydrocarbon distillate fuel oil 96.0

2. An anti-clogging concentrate composition suitable for addition to hydrocarbon fuels normally susceptible toward clogging comprising:

Per cent Dioctyl sodium sulfosuccinate 8 Barium salt of alkyl phenol disulfide 8 Hydrocarbon distillate fuel oil Balance 3. An anti-clogging concentrate composition suitable for addition to hydrocarbon fuels containing substantial amounts of cracked components and normally susceptible toward clogging comprising:

Per cent Dioctyl sodium sulfosuccinate 8 Barium salt of alkyl phenol disulfide 8 Diethylen glycol monobutyl ether 50 Hydrocarbon distillate fuel oil Balance 4. An anti-clogging concentrate composition suitable for addition to hydrocarbon fuels containing substantial amounts of cracked components and normally susceptible toward clogging comprising:

5. An anti-clogging concentrate composition suitable for addition to hydrocarbon distillate fuels containing substantial amounts of cracked components and normally susceptible towards clogging comprising a major amount of a hydrocarbon distillate fuel oil from the group consisting of cracked and mixtures of cracked and straight run fuel oils and a minor amount of from about 2% to about 10% of a metal salt of an unsubstituted sulfoaliphatic dicarboxylic acid ester.

6. An anti-clogging concentrate composition suitable for addition to hydrocarbon distilate fuels containing substantial amounts of cracked components and normally susceptible towards clogging comprising a major amount of a hydrocarbon oil containing a substantial amount of cracked hydrocarbon fractions and a minor amount of from about 2% to about 10% of a salt of an unsubstituted sulfoaliphatic dicar'boxylic acid ester.

7. An anti-clogg concentrate composition suitable for addition to hydrocarbon fuel oils containing substantial amounts of cracked components and normally susceptible towards clogging comprising a major amount of a hydrocarbon fuel and a minor amount. sufficient to inhibit clogging, of a salt of an unsubstituted sulfoaiipnatic carboxylic acid ester.

8. A non-clogging distillate fuel oil containing entrained moisture normally susceptible to cause clogging due to the presence of cracked components in said fuel oil, said fuel oil rendered nonclogging by incorporating therein about 0.005% dioctyl sodium sulfosuccinate, about 0.0042% barium salt of alkyl phenol disulfide and about 0.02b5% diethylene glycol monobutyl ether.

9. A non-clogging distillate fuel oil containing entrained moisture normally susceptible to cause clogging due to the presence of cracked components in said fuel oil, said fuel oil rendered nonclogging by incorporating therein about 0.005% dioctyl sodium sulfosuccinate, about 0.0042% barium salt of alkyl phenol disulfide.

10. A non-clogging distillate fuel oil containing entrained moisture normally susceptible to cause clogging due to the presence of cracked components in said fuel oil, said fuel oil rendered nonclogging by incorporating therein about 0.005% dioctyl sodium sulfosuccinate.

11. A non-clogging distillate fuel oil containing entrained moisture normally susceptible to cause clogging due to the presence of cracked components in said fuel 011, said fuel oil rendered nonclogging by incorporating therein about 0.005% alkali metal salt of an unsubstituted sulfoaliphatic dicarboxylic acid ester.

12. A non-clogging .distillate fuel oil containing entrained moisture normally susceptible to cause clogging due to the presence of cracked components in said fuel oil, said fuel oil rendered nonclosging by incorporating therein from about 0.0025 to about 0.005% of a salt of unsubstituted sulfoaliphatic carboxylic acid ester. 7 13. A non-clogging fuel oil normally susceptible to cause clogging due to presence of cracked components in said fuel oil, said fuel oil rendered nonclogging by incorporating therein -a salt of an unsubstituted sulfoaliphatic carboxylic acid ester in an amount of about one part of said ester to between 25,000 and 50,000 parts of the fuel oil.

CALMY WIES.

JOHN B. R. CARON.

EVERETT B. GLENDENNING.-

12 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES "Aerosol," pub. by 'American Cyanamid 8: Chem. Corp.,'1941, p. 14. 

8. A NON-CLOGGING DISTILLATE FUEL OIL CONTAINING ENTRAINED MOISTURE NORMALLY SUSCEPTIBLE TO CAUSE CLOGGING DUE TO THE PRESENCE OF CRACKED COMPONENTS IN SAID FUEL TO THE PRESENCE OF CRACKED COMPOCLOGGING BY INCORPORATING THEREIN ABOUT 0.005% DIOCTYL SODIUM SULFOSUCCINATE, ABOUT 0.0042% BARIUM SALT OF ALKYL PHENOL DISULFIDE AND ABOUT 0.0265% DIETHYLENE GLYCOL MONOBUTYL ETHER. 